1-Alkanoyloxy-haloethyl urea

ABSTRACT

Herbicidal compounds of the formula   WHEREIN R is alkyl, cycloalkyl or phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkoxy, lower alkyl, or phenoxy, phenylthio or phenylsulfonyl substituted with up to 2 fluorine or chlorine atoms; R1 is hydrogen or alkyl; R2 is alkyl; Z is halogen; Y is hydrogen or Z; and R3 is hydrogen or alkyl.

' United States Patent Singer Oct. 28, 1975 l-ALKANOYLOXY-l-IALOETHYL UREA 3,847,971 11/1974 Koenig et a1 260/490 7 I 51 Inventor 2:35 Scott Smger Rchmond Primary ExaminerRichard L. Raymond Attorney, Agent, or FirmJ. A. Buchanan, Jr.; John [73] Assignee: Chevron Research Company, San Stoner, .lr.

Francisco, Calif. 22 Filed: Dec. 10, 1973 [57] ABSTRACT Herbicidal compounds of the formula [21] Appl. No.: 423,598

Related US. Application Data [63] Continuation-impart of Ser. No. 385,521, Aug. 3, 9

1973, which is a continuation-in-part of Ser. Nos. 124,422, March 16, 1971, abandoned, and Ser. No, I 1 124,423, March 16, 1971, abandoned. R R

[52] US. Cl 260/490; 71/106 wherein R is kyl, cycloalkyl or phenyl substituted [51] Int. Cl. C07C 127/19 with p to 2 fluorine, chlorine. bromine. trifluoro- [58] Field of Search 260/490 y nitro, lower y. lower alkyl, or p y phenylthio or phenylsulfonyl substituted with up to 2 [56] References Cited fluorine or chlorine atoms; R is hydrogen or alkyl; R

UNITED STATES PATENTS is a1ky1; Z is halogen; Y is hydrogen or Z; and R is hy- 3,474,092 10/1969 Dinwoodie et a1 260/490 x dmgen alkyl' 3,498,976 3/1970 Clarke et al. 260/490 X 11 Claims, No Drawings l-ALKANOYLOXY-HALOETHYL UREA RELATED APPLICATIONS abandoned. The disclosure of Ser. No. 385,521 is inlo corporated herein by reference.

DESCRIPTION OF THE PRIOR ART Chattaway et al., Proc. Roy. Soc. (London) A-l34, pp. 372-84 1931 and Chattaway et al., J. Chem. Soc. 1933 30, disclose compounds prepared by the condensation of chloral with aryl ureas, and the acetylation of the resulting condensation products with acetic anhydride to produce diacetyl ureas and/or bis-ureido ethers.

US. Pat. No. 3,040,082 and I-Ioover et al., J. Org. Chem. 28(7), l825- (1963) disclose ,B-polyhalo-ahydrocarbyl isocyanates and derivatives thereof, such as l(1-hydroxy-2,2,2-trifluoroethyl)-3-pheny1 urea and l( 1-hydroxy-2,2,2-trichloroethyl)-3-phenyl urea, and their use as herbicides.

Also, U.S. Pat. Nos. 2,846,399, 2,902,356, 3,418,334 and 3,488,376 disclose ureas and their uses.

DESCRIPTION OF THE INVENTION Compounds of the present invention may be represented by the formula (I) wherein R is alkyl of l to 12 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, or phenyl substituted with up to 2 (O to 2) fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkoxy, lower alkyl, or phenoxy, phenylthio or phenylsulfonyl substituted with up to 2 fluorine or chlorine; R is hydrogen or alkyl of 1 to 4 carbon atoms; R is alkyl of l to 4 carbon atoms; Z is chlorine or bromine; Y is hydrogen or Z; and R is hydrogen or alkyl of l to 6 carbon atoms.

Preferably R is alkyl of l to 6 carbon atoms, cycloalkyl of 5 to 6 carbon atoms or phenyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkoxy or lower alkyl groups. More preferably, R is phenyl substituted with 1 to 2 fluorine or chlorine. A single trifluoromethyl or fluorine group is preferably attached to the phenyl in the ortho position. Preferably Y is chlorine or bromine, R is hydrogen and R is alkyl of l to 4 carbon atoms. More preferably R is methyl. R is preferably hydrogen.

Representative groups which R may represent include methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, sec.butyl, decyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, 2-fluorophenyl, 2- chlorophenyl, 2-chloro-4-bromophenyl, 3-methylphenyl, 4-methoxyphenyl, 2-nitrophenyl, 2-trifluoromethylphenyl, 4-phenoxyphenyl, 4-phenylthiophenyl, 4- phenylsulfonylphenyl, and 4-(2-chlorophenoxy)phenyl.

2 Representative alkyl groups which R, R and R may represent include hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, hexyl, etc.

Representative compounds of the invention include:

1-methy1-l-( 1-formyloxy-2,2,2-trichloroethyl)-3-(4- phenoxyphenyl urea, l-methyl-1-( l-formyloxy-2,2,2-trichloroethyl )-3-( 4- [4-chlorophenoxyl]phenyl) urea, l-ethyll l-formyloxy-2,2,2-tribromomethyl )-3-(4- phenylsulfonylphenyl) urea,

l-methyl-1-( l-formyloxy-2,2,2-trichloroethyl )-3-phenyl urea,

1-ethyll 1-formyloxy-2,2,2-trichloroethyl )-3-( 2-trifluoromethylphenyl) urea,

l-methyll( 1-formyloxy-2,2,2-tribromoethyl-3-( 2- fluorophenyl) urea,

l-butyll 1-formyloxy-2,2-dichloro-2-bromoethyl )-3- (2-nitrophenyl) urea, 1-methyl-1-( 1-formyloxy-2,2-dichloroethyl)-3-( 4- methylphenyl) urea, l-butvll l-formyloxy-2,2,2-trifluoroethyl )-3-( 4- methoxyphenyl) urea,

l-methyll l-formyloxy-2,2,2-trichloroethyl)-3- methyl urea,

l-methyll( 1-formyloxy-2,2,2-trichloroethyl)-3-dodecyl urea,

l-methyl-1-( l-formyloxy-2,2,2-trichloroethyl)-3- cyclopentyl urea,

l-methyll( l-propionyloxy-2,2,2-trichloroethyl )-3- cyclohexylurea,

l-methyll( l -formyloxy-2,2,2-trichloroethyl)-3-( 4- phenylthiophenyl) urea,

1-rnethyl-l-( l-formyloxy-2,2,Z-trichloroethyl )-3-( 2- bromophenyl) urea,

l-methyl-1-( l-acetoxy-2,2,2-tribromoethyl )-3-( 2 chlorophenyl) urea,

l-methyll( l-acetoxy-2,2,2-trichloroethyl)-3-(4- nitrophenyl) urea,

l-methyll( l-acetoxy-2-bromo-2,2-dichloroethyl)-3- (3-chloro-4-methoxyphenyl) urea, l-methyll 1-propionyloxy-2,2,2-trichloroethyl)-3- (2-fluorophenyl) urea, lmethyll( l-butyrylo xy-2-bromo-2,2-dichloroethyl 3-(3-chlorophenyl) urea, l-methyll( l-pentanoyloxy-2,2-dichloroethy1)-3- (2,4-dichlorophenyl) urea, l-methyll( l-n-hexanoyloxy-2,2,2-trichloroethyl )-3- (2-nitrophenyl) urea, and l-ethyll l-acetoxy-Z, 2,2-trichloroethyl )-3-( Z-methyl-4-chlorophenyl).urea.

The preferred compounds of the invention are those wherein R, R and R are as defined above, R is hydrogen and Y and z are chlorine.

The preparation of compounds of the present invention begins with the a-hydroxy compounds represented by formula (IV). Such compounds are prepared by reacting a urea with an aldehyde according to the following reaction (1) o 0 0 on II II II I R-N-C-NH HC-CZ2Y RNCN-CIl-CZ Y (1) (II) (III) (IV) wherein R, R, R Y and Z are as defined above.

The urea reactants (ll) employed for reaction l are known compounds of the prior art. The aldehyde ([11) may be a compound such as chloral (trichloroacetaldehyde), dichloroacetaldehyde, dichlorobromoacetaldehyde, tribromoacetaldehyde, etc. Reaction (1) may be accomplished in the presence of a solvent or neat. Generally, stoichiometric amounts of the urea and aldehyde will be used. A small amount of acid, preferably sulfuric acid or perchloric acid, may be used. The reaction temperature will be from 20 to 100C. Generally the reaction proceeds very rapidly and will be complete in a matter of a few minutes. Reaction times of from 30 seconds to hours are considered sufi'lcient.

The a-hydroxy compound (IV) is then converted to the a-chloro compound represented by formula (V) by reacting the a-hydroxy compound (IV) either in purified fonn or in the reaction mixture of reaction 1 with thionyl chloride according to the following reaction I l R-N-C-N-CH-CZ2Y socl I I R R2 (xv) I1 I R-N-C-NCHCZ2Y $0 RC1 I l R R (V) wherein R, R, R, Y and Z are as defined above.

The reaction (2) can be accomplished by using from a molar amount of thionyl chloride to an excess of as much as mols, based on the urea. The reaction temperature will be from 20 to 100C. and reaction time will be from 1 to 20 hours. lf desired, reactions l) and (2) may be combined to prepare the a-chloro compound (V) by simply mixing together the urea reactant (ll), the aldehyde reactant (Ill) and the thionyl chloride. The a-chloro product (V) can be recovered by slurrying in a solvent such as diethyl ether or methylene chloride, collecting the product on a filter, then purifying by recrystallizing from inert solvents such as a 1:1 mixture of l,2-dimethoxymethane and methylene chloride or a 1:1 acetone and methylene chloride mixture.

The compounds of the present invention are prepared by reacting the a-chloro compound (V) with ammonium formate or alkanoate as shown in reaction (3) below:

0 c1 0 R-u-c-I-cu-cz .0510

I o oclz I I n-u-c-n-cu-cz,y lligcl wherein R, R, R, R, Z and Y are as defined above.

The above reaction (3) can be accomplished readily by mixing the reactants preferably in a solvent such as l,2dimethoxyethane in an amount from 2 to 50% by volume for a time from about 0.25 to 20 hours at a temperature from about 20 to C. The solvent is then removed and the product is isolated and purified by conventional methods such as extraction, filtration, recrystallization, etc. Generally thev ammonium formate or alkanoate will be in excess, in an amount of 5 to 100% of the a-chloro urea reactant (V).

The formyloxy-substituted ureas of formulas (I), (II) or (III) can also be prepared by reacting the a-chloro compound (V) with formic acid in the presence of an acid acceptor, according to the following reaction (4):

0 0 0E a-n-c-r i-cwz y B-l-ICl (VII) wherein R, R, R, Z and Y are as defined above and B is an acid acceptor.

The above reaction (4) is readily accomplished by contacting a-chloro urea (V) with an excess of formic acid of up to 20 mols, based on the urea (V), at a temperature of 0 to 50C. Suitable acid acceptors are organic nitrogen bases having no free N-H groups such as trialkylamines, e.g., trimethylamine and triethylamine, and pyridine compounds, e.g., pyridine and 2-methylpyridine. The molar ratios of acid acceptor to urea (V) is substantially equimolar, e.g., 1.5:1 to l:l.5. The aformyloxy product (Vll) is isolated and purified by conventional methods such as filtration, extraction, crystallization, etc.

The present invention will be more fully understood by reference to the following examples.

EXAMPLES Example 1 Preparation of l-methyl-l-( l-hydroxy-2,2,2-trichloroethyl)-3-phenyl urea I l-methyl-3-phenyl urea (7.5 g, 0.05 mol) was reacted with 7.5 g (0.05 mol) of chloral without solvent. The mixture was shaken for a short period of time. After, three drops of perchloric acid were added and the mixture heated gently for a few minutes to give a homogeneous viscous oil. Upon cooling, the product formed as a glass. The chemical analysis showed: %Cl, calculated 35.8, found 35.8; %N, calculated 9.4, found 8.0. The product is the fifth compound tabulated in Table 1.

Example 2 Preparation of l-methyll l ,2,2,2-tetrachloroethyl 3-( Z-fiuorophenyl) urea N-methyl-N'-o-fluorophenyl urea (16.8 g, 0.1 mol) was combined with 22.5 g (0.15 mol) chloral and 18.0 g (0.15 mol) thionyl chloride. After several minutes and exothermicity was noted and the reaction mixture became a homogenous yellow oil. After five minutes more, a precipitate beganto form. After 1% hours a 3:1 mixture of diethyl ether:petroleum ether wsa added and the product was collected on a filter and dried. The product weighed 25 g, melted at 130-l4lC.- and analyzed as follows: %Cl, calculated 35.7, found 37.3; %N, calculated 9.5, found 9.5. The product is the sixth compound tabulated in Table 1.

Example 3 Preparation of l-methyll 1,2,2,2-tetrachloroethyl)- 3-(3,4-dichlorophenyl) urea l-(3,4-dichlorophenyl)-3-methyl urea (15.2 g, 0.07 mol) was combined with 15.0 g (0.1 mol) of chloral and 5 drops of concentrated sulfuric acid. The mixture was heated for an hour to effect reaction, then stripped under vacuum. To the crude 1-(3,4-dichlorophenyl)-3- (1-hydroxy-2,2,2-trichloroethyl)-3-methyl urea was added an excess of thionyl chloride and the mixture was heated gradually to a maximum of 65C. Diethyl ether was added to the crude product, and the insoluble product was collected on a filter, washed twice with diethyl ether and dried. The 15.3 g of product, which melted at 132l40C., analyzed as follows: %Cl, calculated 55.2, found 46.0. The product is the seventh compound tabulated in Table 1.

Example 4 Preparation of l-methyl-l 1,2,2,2-tetrachloroethyl)-3- (4-phenoxyphenyl) urea.

p-Phenoxyaniline (11.7 g, 0.063 mol) was dissolved in 25 m1. 1,2-dimethoxyethane (Ansul E-l21) and heated to 65C. Methyl isocyanate (3.7 g, 0.65 mol) was added over a period of minutes. Heating and stirring were continued for 1 hour. Then chloral (14.8 g, 0.1 mol) was added to the hot solution, followed immediately by the addition of 11.9 g (0.1 mol) thionyl chloride. It was kept at 65C. for 4% hours. The solution was cooled to 40, and 25 ml of methylene chloride was added. The solution was refluxed for one more hour and then allowed to cool. The solid which formed upon cooling was filtered, washed with methylene chloride to give 5.0 g (20% yield) of the product, as a white powder, melting point l65-167C. A second crop, melting point l60-162C., weighed 5.5 g (22%). Elemental analysis showed: %Cl, calc. 34.8, found 34.4; %N, calc. 6.9, found 6.8; %C, calc. 47.1, found 47.5; %l-l, calc. 3.46, found 3.3. The product is the eighth compound tabulated in Table 1.

Example 5 Preparation of l-methyl- 1 l-formyloxy-2,2,2-trichloroethyl -3-( 3 ,4-dichlorophenyl) urea Triethylamine (2 g, 0.02 mol) was added slowly to a slurry of 4.4 g (0.02 mol) l-methyl-l-(l,2,2,2-tetrachloroethyl)-3-(3,4-dichlorophenyl) urea in 50 ml formic acid. After stirring for about minutes, a precipitate of triethylamine hydrochloride formed. The reaction mixture was then poured into 300 ml water, filtered and dried. The resulting crude product melted at 136145C. The crude product was then diluted with l5-20 ml benzene and filtered. The filtrate was concentrated to about 10-15 ml and diluted with 50 ml hexane to precipitate the product as a while solid, m.p. l38l40C. Analysis was as follows: %C, calc. 33.5, found 33.8; %l-l, calc. 2.3, found 2.1; %N, calc. 7.1, found 7.1. The product is the first compound tabulated in Table 1. Example 6 Preparation of l-methyl- 1 1-acetoxy-2,2,2-trichloroethyl)-3-(3,4-dichlorophenyl) urea 1-methyl-1-(1,2,2,2-tetrach1oroethyl)-3-(3,4- dichlorphenyl) urea (7.7 g, 0.02 mol) was dissolved in 200 m1 dimethoxyethane, followed by the addition of 1.5 g of ammonium acetate. The mixture was stirred for 2 hours, filtered, and stripped of solvent. The residual mush was added to ether and the etherinsoluble material filtered off. Next, the ether was removed under vacuum. The residual oil was added to chloroform and some undissolved material was removed by filtration. The filtrate was evaporated to give 5.5 g of the product, as an oil. The infrared and NMR spectra were consistent with the assigned structure. The chlorine analysis was: %Cl, calc. 43.5, found 41.7. The product is the third compound tabulated in Table 1.

Other compounds and intermediates of the present invention were prepared using the methods as described above. These compounds are listed in Table I.

UTILITY The ureas of the present invention are, in general, herbicidal in both preand post-emergent applications. For preemergent control of undesirable vegetation, these ureas will be applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergent applications, the ureas of the present invention will be applied directly to the foilage and other plant parts. Generally they are effective againstweed grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

Preand post-emergent herbicidal tests on representative ureas of this invention were made using the following methods:

Pre-Emergent Test Acetone solutions of the test ureas were prepared by mixing 750 mg urea, 220 mg of a nonionic surfactant and 25 ml of acetone. This solution was added to approximately 125 ml of water containing 156 mg of surfactant.

Seeds of the test vegetation were planted in a pot of soil and the urea solution was sprayed uniformly onto the soil surface at a dose of mcg per cm The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc., for a 3 week period. At the end of this period, the herbicidal effectiveness of the urea was rated, based on the physiological observations. A O-tol 00 scale was used, 0 representing no phytotoxicity, 100 representing complete kill.

Post-Emergent Test The test ureas were formulated in the same manner as described above for the pre-emergent test. The concentration of the urea in this formulation was 5000 ppm. This formulation was uniformly sprayed on similar pots of 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 100 mcg per cm. After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases, as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the urea was rated, based on these observations. A 0-to-l00 scale was used, 0 representing no 7 phytotoxicity, 100 representing complete kill.

The results of these tests appear in Table II. The amount of urea administered will vary with the particular plant part or plant growth medium which is 8 used. Such application is equivalent to about 0.5 to 20 lbs urea per acre.

The herbicidal compositions of this invention comprise an herbicidal amount of one or more of the to be contacted, the general location of application. above-described ureas intimately admixed with a bloi.e., sheltered areas such as greenhouses as compared logically inert carrier. The carrier may be a liquid diluto exposed areas such as fields as well as the desired ent, such as water or acetone, or a solid. The solid may type of control. For pre-emergent control of most be in the form of dust powder or granules. These complants, dosages in the range of about 0.5 to lbs per positions will also usually contain ad uvants such as 3 acre will be used. Such administration will give a con- 10 wetting or dispersing agent to facilitate their penetracentration of about 2 to ppm urea distributed tion into the plant growth medium or plant tissue and throughout 0.1 acrefoot. For post-emergent applicagenerally enhance their effectiveness. These composition, such as foliar spray application, compositions contions may also contain other pesticides, stabilizers, containing about 0.5 to 8 lbs urea per gals spray will be ditioners, fillers, and the like.

TABLE I Elemental Analysis Melting Halogen N S Point. Compound Calc. Found Cale. Found Cale. Found C.

1 -methy1- l 1-fonny1oxy-2,2,2-trich1oroethyl3-( 3,4-dich1orophenyl) urea 7.1 7.1 138-140 1 -methyl- 1 1 -formy1oxy-2,2,Z-trichloroethyl )3-( Z-fluorophenyl) urea 38.4 38.8 124-127 1-methy1-1-( 1-acetoxy-2,2,Z-trichloroethyl )-3-( 3 .4-dich1orophenyl) urea 43.5 41.7 oil l-methyl- 1-( 1-acetoxy-2.2,2-trieh1oroethyl )-3-( 3-ch1orophenyl) urea 38.0 34.6 7.5 7.0 -152 l-methy1-1-( 1-hydroXy-2.2.2-trich1oroethy1)-3-pheny1 urea 35.8 35.8 9.4 8.0

1-methyl-1-( 1.2,2,2-tetrach1oroethy1)-3-(2-fluorophenyl) urea 35.7 37.3 9.5 9.5 130-141 1methy1-l-( 1.2.2.2-tetrach1oroethyl )-3-( 3.4-dich1oropheny1) urea 55.2 46.0 132-140 1-methy1-1-( l.2,2,2-tetrachloroethyl)-3-(4-phenoxypheny1) urea 34.8 34.4 6.9 6.8 -167 1-methy1-1-( 1,2,2.2-tetrach1oroethy1)-3-(2-ch1orophenyl) urea 45.2 49.4 139-145 1-methy1-1-( 1.2,2,2-tetrach1oroethy1)-3-(4-ch1oropheny1) urea 45.2 41.9 -180 1-rnethy1-l-( 1 .2,2,2-tetrach1oroethy1)-3-(2,4-dich10ropheny1 urea 45.5 43.6 -193 1-methy1-1-(1,2,2,2-tetrach1oroethy1)-3-(4-bromopheny1) urea' 12.7 13.4 187-190 1-methy1-1-(1,2.2,2-tetrach1oroethy1)-3-(3-ch1oropheny1) urea 50.6 50.0 8.0 7.3 155-160 l-methy1-l-( 1,2,2.2-tetrach1oroethy1)-3-pheny1 urea 44.9 34.4 8.9 8.4 164-166 1-methy1-1-( l ,2,2.2-tetrach1oroethy1)-3-( 3-ch1oro-4-bromophenyl) urea 14.0 13.7 6.5 6.2 189-190 1-methy1-1-( 1-hydroxy-2.2,2-trich1oroethyl )-3-( 3-ch1orophenyl) urea 42.8 39.4 8.4 9.5 oil 1-methy1-1-( 1,2,2,2-tetrach1oroethy1)-3-(2-trifluoro- CI 30.6 30.9

methylphenyl) urea F 16.4 16.2 145-148 1-methy1-1-( 1 ,2,2,2-tetrach1oroethy1)-3-(3,5-dich1orophenyl) urea 55.4 50.3 7.3 7.5 150-157 1 -methyl- 1 1,2.2-trieh1oro-2-bromoethy1)-3-( 2-fluorophenyl) urea 10.6 10.5 139-142 1-methy1-1-( 1-bromo-2,2,2-trich1oroethy1)-3-( Z-fluorophenyl) urea Br 21.2 21.5 153-155 1-methy1-1-( 1,2,2,2-tetrach1oroethy1)-3-(4-methoxyphenyl) urea 41.1 40.1 8.1 8.2 176-179 1-methy1-1-( 1.2,2-trich1oro-2-bromoethyl)-3-( 3,4-

dichlorophenyl) urea 14.0 13.8 166-169 1-methy1-1-( 1 ,2,2-trich1oro-2-bromoethy1)-3-( 3-chlorophenyl) urea CI 9.0 8.4 150-152 1-methyl-1-( 1,2.2,2-tetrach1oroethy1)-3-( 3-trifluoro- C1 9.3 9.2

methylphenyl) urea F 14.8 14.9 138-142 1-methy1-1-( 1,2-dibromo-2,Z-dichloroethyl)-3-( 2-fluorophenyl) urea Br 19.5 16.2 6.8 7.5 130-133 1-methy1-1-( 1 ,2.2,2-tetrach1oroethy1)-3-[3-methy1- 4-(4'-chloropheny1thio)phenyl] urea 37.5 35.4 6.8 6.8 152-154 l-methy1-1-( 1,2.2.2-tetrach1oroethy1)-3-[3-methy1-4-(4- chlorophenylsulfonyl)phenyl] urea 35.1 29.0 6.3 6.8 168-171 l-methy1-1-(1,2,2-trich1oroethy1)-3-(3-ch1oropheny1) urea 8.9 8.9 38.0 38.0 118-127 phenoxy)phenyl] urea 40.1 39.6 6.3 6.3 153-156 1methy1-l-( 1-hydroxy-2,2,2-trich1oroethy1)-3-(3-pyridy1) urea 35.6 32.2 14.1 12.0 oil 1-methy1-1-( 1 -hydroxy-2,2.2-trich1oroethy1)-3-( Z-thiazolyl urea 34.9 35.8 oil 1-methy11-( 1-hydroxy-2.2,2-trich1oroethy1)-3-(2-pyridy1) urea 35.6 33.6 il

1-methy1-1-( 1-hydroxy-2,2,2-trieh1oroethy1)-3-(2-pyrimidy1) urea 35.5 35.4 18.7 18.2 100-104 1-methy1-1-( 1,2,2,2-tetrach1oroethyl)-3-cyc1openty1 urea 9.1 8.7 132-136 1-methy1-1-( l,2,2,2-tetrach1oroethy1)-3-cyclohexy1 urea 87 8.4 127-1295 1-methy1-l-( 1,2,2.2-tetrach1oroethy1)-3-methy1 urea 1 1.0 10.9 73-76 1-methy1-1-( 1,2,2,2-tetrach1oroethy1)-3-n-hexy1 urea 8.7 9.2 45-55 1-methy1-1-( 1,2,2,2-tetrach1oroethyl)-3-t-buty1 urea 9.5 9.7 32.5 31.7 84-88 1-methy1-1-( I,2,2,2-tetrach1oroethy1)-3-n-dodecy1 urea 34.7 33.5 6.9 6.3 39-41 1-methoxy-1-( 1 ,2.2.2-tetrach1oroethy1)-3-( 2-fluoro- CI 40.6 40.2

phenyl) urea F 5.4 5.8 75-78 l-methy1-1-( 1-chloro-2.2.2-tribromoethy1)-3-( 3 ,4-dieh1oro- 1 1 What is claimed is: l. A compound of the formula I o-c-R ll R--NCN--CH--CZ ZY wherein R is alkyl of 1 to 12 carbon atoms, cycloallgyl of 3 to 8 carbon atoms, phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkyl, lower alkoxy, or phenylthio, phenoxy or phenylsulfonyl substituted with up to 2 fluorine or chlorine groups; R is hydrogen or alkyl of l to 4 carbon atoms; R is alkyl of 1 to 4 carbon atoms; Z is chlorine or bromine; Y is hydrogen or Z, and R is hydrogen or alkyl of l to 6 carbon atoms.

2. The compound of claim 1 wherein R and R are hydrogen.

chlorine.

4. The compound of claim 3 whereirrR is phenyl substituted with l to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkoxy or lower alkyl.

5. The compound of claim 4 wherein R is phenyl substi'tuted with 1 to 2 fluorine or chlorine.

6. 1-Methyl-l( l-formyloxy-2,2,2-trichloroethyl)-3- (Z-fluorophenyl) urea, according to claim 5.

7. 1-methyl-l-( l-formyloxy-2,2,2-trichloroethyl )-3- 3,4-dichlorophenyl urea, according to claim 5.

8. The compound of claim 1 wherein R is hydrogen, R is alkyl; and Z and Y are chlorine.

9. The compound of claim 8 wherein R is phenyl substituted with l to 2 fluorine, chlorine, bromine, trifluo- 'romethyl, nitro, lower alkoxy or lower alkyl.

10. The compound of claim 9 wherein R is phenyl substituted with 1 to 2' fluorine or chlorine.

l 1 l-Methyl-1-( 1-acetoxy-2,2,2-trichloroethyl )-3- (3,4-dichlorophenyl), according to claim 10. 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein R1 and R3 are hydrogen.
 3. The compound of claim 2 wherein Z and Y are chlorine.
 4. The compound of claim 3 wherein R is phenyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkoxy or lower alkyl.
 5. The compound of claim 4 wherein R is phenyl substituted with 1 to 2 fluorine or chlorine.
 6. 1-Methyl-1(1-formyloxy-2,2,2-trichloroethyl)-3-(2-fluorophenyl) urea, according to claim
 5. 7. 1-methyl-1-(1-formyloxy-2,2,2-trichloroethyl)-3-3,4-dichlorophenyl urea, according to claim
 5. 8. The compound of claim 1 wherein R1 is hydrogen, R3 is alkyl; and Z and Y are chlorine.
 9. The compound of claim 8 wherein R is phenyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, lower alkoxy or lower alkyl.
 10. The compound of claim 9 wherein R is phenyl substituted with 1 to 2 fluorine or chlorine.
 11. 1-Methyl-1-(1-acetoxy-2,2,2-trichloroethyl)-3-(3,4-dichlorophenyl), according to claim
 10. 